CAS号 [117-80-6] 生产工艺。   2,3-二氯萘醌

CAS名：1,4-Naphthoquinone, 2,3-dichloro-     历史参考文献：Beil. 7, 729; E1, 386; E2, 653; E3, 3703; E4, 2426.

用途：催化剂。农药。染料：还原黄27。LookChem网登录生产与经营单位94家。  反应类别：氯化。

BIOS 1152, 125-128.（=胶卷PB 81027）。 2,3-Dichloronaphthoquinone. (Ludwigshafen).  英国人译自德文（无资料来源）。

反应式：本人有加注，有德文原件，但本人未抄录。

Outline: α-Naphthoquinone is chlorinated in nitrobenzene.   Theoretical yield 100 parts naphthoquinone give 144 parts dichloronaphthoquinone. 

Plant yield 100 parts à 120 parts equivalent to 83.4% theory.

Time of operation:  操作周期：30 hours.    Daily output: 日生产能力：120 kg. at 100%.

Plant: 设备： 1.5 m3 stirred pressure vessel, lead-lined, with steam jacket.  Individual drive, blade agitator, 90 r.p.m.

3 m2 Nutsche, leaded, ‘Pantel’ tiles with Hochst cement, SW. 10’.    Lead-lined receiver 2 m3.

Process: 操作步骤：

The chlorinator is charged with 900 kg. of nitrobenzene (dry), and then 200 kg. of α-naphthoquinone dry at 100% are charged in carefully to avoid formation of lumps.  The mixture is stirred for 0.5-1 hour at room temperature, and 2.8 kg. of iron powder then added carefully over 15 min.  Chlorination is started with cold water at 20℃. circulating through the jacket.  A total of 400 kg. of chlorine is charged at the rate of 50 kg./hour, with gradual increasing temperature, as follows:  Time:      Temp. ℃.   Chlorine added.    续左： Time:    Temp. ℃.    Chlorine added .

                  Start       15-20        0                      5      55-57       250

              After 1 hr.       23-25       50                      6      69-70       300

                   2         30-32      100                      7      81-83       350

                   3         36-38      150                      8      94-96       400

                   4         43-45      200

To achieve these temperatures, the cooling water is shut off after the introduction of 150-200 kg. chlorine; then steam is introduced carefully as required.

When all the chlorine has been introduced, a sample is taken (test below).  When the test is satisfactory, the batch is cooled with agitation to 20℃.  During this cooling period, a stream of nitrogen is passed through the batch, via the chlorine inlet pipe, to remove excess chlorine and hydrochloric acid gas and to prevent the crystallization of the product in the inlet pipe.  From time to time during the cooling, the crystals on the walls of the vessel are scraped off by means of a wooden shovel.

The product is dropped to the tiled-nutsche and the chlorinator washed out with 250 kg. of the filtrate.  The nutsche cake is pulled as dry as possible but not washed.  The nitrobenzene-wet paste is charged into lead-lined tubs for transference to other parts of the works for the conversion to Indanthrene Gleb 6GD and Indanthrene Fabr. Lu. 467.  A sample is analysed.

The nitrobenzene filtrate, after treating with soda, is recovered by distillation.

Yield: = 320 kg. 2,3-dichloronaphthoquinone paste at 75% = 240 kg. at 100% = 120% by wt. on naphthoquinone. = 83.4% theory.

Notes on Process:  操作要点：

1.  Naphthoquinone is normally obtained as a moist filter-cake and must be dried before use in a Venuleth dryer at 40-45℃. with good vacuum (40 mm.).  If higher temperatures are used polymerization may occur.  

 2.  Naphthoquinone forms an addition compound with chlorine which, in the absence of excess chlorine and on application of heat, readily polymerises.  The chlorination must therefore not be interrupted once it has begun.  The reaction normally proceeds via this addition compound, which in the presence of excess chlorine loses one mol. of hydrochloric acid and forms 2-chloro-α-naphthoquinone.  This by direct chlorination then gives the desire 2,3-dichloronaphthoquinone.  For the above reasons the temperature and rate of chlorination given in the process must be strictly adhered to.  Under the microscope the addition compound (precipitated by cooling the nitrobenzene solution) appears as colourless crystals, whereas the final product is yellow.

Samples and Tests: 取样和样品的测试：

A sample is taken after completion of chlorination, cooled, filtered, washed with benzene and then with ligroin and finally dried.  The product should be in the form of bright yellow prisms of m. p. 190-198℃.

The mother liquor when heated with alcoholic caustic soda must give an orange-red coloured solution; the intermediate products if present give a dirty brown colour.

The naphthoquinone used must be 70% strength; the naphthalic and phthalic acid contents are determined and also the strength by reduction with TiCl. (2 H required).

Solvent Lose: 溶剂损耗量： Nitrobenzene lost = 200 kg. = 22% of that charged.

Of this, some 75 kg. are recovered from the product at a later stage in the conversion to dtestuff.

Disposal of hydrochloric acid gas and chlorine:  The waste gases are led via the fume duct to an absorber.

Quality of 2,3-Dichloronaphthoquinone:  Impurities present: Iron, lead, polymerization products

Estimation of strength: 产品的测定方法：

20 g. of the sample are dissolved in 150 cc. of o-dichlorobenzene.  The solution is filtered to remove impurities, and, after addition of 15 cc. 400Be’ caustic liquor, is steam-distilled.  This gives an orange-red coloured solution of the sodium salt of 2-chloro-3-hydroxynaphthoquinone.  The solution is screened and the product precipitated with hydrochloric acid, filtered, washed with cold water, dried and weighed (wt. = a g.).

% 2,3-Dichloronaphthoquinone in product  227 x 100 x a / 208.5 x 20.  The 2-chloro-3-hydroxynaphthoquinone should melt at 214-218℃.

细田豊 《理论制造染料化学》 1957年。 P. 546.  2,3-Dichloro-1,4-naphthoquinone.  译自PB 70057.（未说明页号。）。

1.5 m3铅张釜でニトロベンゼン900 kgにα-ナフトキノン（100%）200 kgを入れ，0.5-1 h搅拌後铁粉2.8 kg添加，Cl2 400 kgを50 kg/hの速さで导入，温度は冷却しながら200より入れ始めしだいに上升して最後には94-960に至らしめる。反应终ればCl2を止めてN2ガスを通じHCl を追出しながら结晶させ滤過し，そのままインダンスレンエロ – 6GD用いる。ニトロベンゼンペ - ト320 kg （75%）= 240 kg (100%)。

张澍声 《精细化工中间体工业生产技术》1996年。 P. 223-224.  2,3-二氯-1,4-萘醌。 译自BIOS 1152, 125和PB 70057。

2,3-二氯-1,4-萘醌：在1500 L锅中加入900 kg硝基苯，再加入200 kg 100% 1,4-萘醌，搅拌0.5-1小时，加入2.8 kg铁粉，冷至20℃，以50 kg/hr的速度导入400 kg氯气。在冷却下温度仍在上升，从20℃最后升至94-95℃。反应完毕后，停止通氯，通氮气排出氯气和氯化氢，过滤出320 kg 2,3-二氯-1,4-萘醌的硝基苯滤饼，含量75%，相当于240 kg 100%，收率83.4%。

PB 70057, 8625-8630.  2,3-Dichloro-1,4-naphthoquinone, moist calculation 100%. By Schneider.  1939年2月27日德文生产工艺。

    本人未抄录。日人细田豊和张澍声老先生均未说明页号。本胶卷，上海染料研究所有放大本，是从北京复制的。

PB 70342.  Reports on dyes and dye intermediates.  951页。1934-1942年德文生产工艺。沈阳院有进口胶卷。

PB 70342, 14380-14382.  Drying of 2,3-dichloro-1,4-naphthoquinone. By Müller.  1938年11月11日德文生产工艺。未抄录。

国内研究动态：

王绍兴 （天津市染料工业研究所）。  2,3-二氯-1,4-萘醌的合成方法。 [J] 染料工业, 1990, 6, 21-23.

研究了7种合成方法，最后说明以甲萘胺盐酸盐为原料合成2,3-二氯-1,4-萘醌为最好的方法。本文不再抄录，请读者看原刊物。

参考文献：18篇，未引用上述历史资料。

国内出版物：

侯乐山 主编 《中国精细化工产品集 – 原料及中间体 10396种》2006年。 P. 435.  2,3-二氯-1,4-萘醌。

中国化工信息中心  全国精细化工原料及中间体行业协作组 出版 《版权所有  未经允许  不得翻印》。

2,3-二氯-1,4-萘醌：（其它项目暂不抄录！）

生产方法：由1,4-萘醌氧化而得。

氧化操作在乙酐或二硝基苯或醇类，酚类，碳氢化合物溶剂中进行，催化剂为溴素或铁粉和氯化铁。 也可由1,4-氨基萘磺酸在50%稀硫酸中，以铁为催化剂，在80℃进行氯化而得。

何岩彬 主编 《染料品种大全》 沈阳出版社 出版。 2018年。P. 1851-2038.  染料中间体及可合成的染料。

P. 1920. 中文名称：2,3-二氯-1,4-萘醌。

老有所为，老有所乐。乐在还能抄录一些读者认为是《考古》的资料。如果还能有点利用价值，那是最好的了！谢谢各位！

陈忠源 2019年3月19日星期二。